New compounds of the thiazolic series



Patented n. 30, 1930 UNITED STATES PATENT? OFFICE HANS PAUL xAUmAnn, or JENA, AND MAX scnunnnr, or FRANKFOBT-ON-THE- uAm-rncmmnnm, GERMANY, AssIeNons'ro-r. e. FARBENINDUSTRIE Axrrnn- GESELLSOHAFT, or FRANKFORT-ON-THE-MAIN, GERMANY, A CORPORATION or GER- MANY I NEW COMPOUNDS OF THE THIAZOLIC SERIES No Drawing. Original application filed April 12, 1927, Serial 1T0. 183,228, and in Germany April 15, 1926.

' Divided and this application'filed August 28, 1829. Serial No. 388,028.

This application is a division of our application Serial No. 183,228, filed April 12, 1927.

Our invention relates to new compounds containing sulfur, having probably in the1r molecule a. thiazol ring and corresponding to the general formula:

or its tautomeric form N\ ary1 CNH:

wherein aryl means an aromatic residue of the benzene, naphthalene, anthracene or 15 anthraquinone series, which may contain further substituents, which products may be obtained by allowing a salt of sulfocyanic acid to act on primary arylamines, in which the para-position to the ammo-group 1s 30 either substituted by a monovalent radlcle or blockaded (as f, i. in the case of ,8- naphthylamine), in the presence of a Sultable halo en (Cl or Br) and preferably 1n an acidic'me ium.

The reaction runs probably in such a way, that in the first phase ortho-aminosulfocyanic compounds of the general formula:

are formed, which by the influence of the acidic medium or of the acid resulting from the reaction are converted into the isomeric aminothiazolic compounds, either in statu =5 nascen-di or after standing for some time or warming of the acidic reaction mass. By treating the separated QIthO-tLIIlIXIOSlllfO- cyanic compounds with dilute acids or by heating them preferably h1gher than the1r melting point they are converted into the aminothiazolic compounds. The new th azolic compounds are mostly crystalline bodies, having a definite melting point, they possess a bas1c character, but the r ammo- 5 group is masked in most cases, as indlcated by the aforesaid first formula for these compounds, because the new compounds yield in most cases, when diazotized in the usual manner, compounds having only a weak capacity for coupling with the usual azodyestuff components.

The new compounds are valuable intermediates for the production of dyestuffs and pharmaceutical products. I The following example will further illustrate our invention, but it is understood, that our invention is not limited to the particular proportions, reacting conditions or materials listed therein.

Ewample 9 parts of para-phenetidine are mixed with about 120 arts of 96% acetic acid and 18 parts of so ium sulfocyanide. Then a solution of 9 parts of bromine in 20 parts of acetic acid is slowly added at ordinary temcrature. The product of reaction separates roin the mixture in colorless crystals. It is filtered and washed with a solution of sodium carbonate and for purifying, it is redissolved in dilute hydrochloric acid and precipitated with a solution of a suitable alkali. The product of reaction shows, when recrystallized from. dilute spirit, a melting point of 163 C. It corresponds probably to the formula C-NH1 CzHaO S The new compound is quite soluble in hydrochloric acid and yields with nitrous acid a yellowish diazo compound, which couples with resorcinol to a red, with H-acid to a blue, with 2-naphthol-7-sulfonic acid to a reddish violet azodyestufi.

We claim: I

As a new product a compound containing sulfur, having probably a thiazole ring in its molecule and corresponding probably to the which is when dry a crystalline substance, meltin at about 163, when recrystallized from ilute spirit, and yielding a yellowish diazo compound.

In testimony whereof, we aflix our signatures.

HANS PAUL KAUFMANN. MAX SGHUBERT. 

